Method of increasing the sugar content of sugar cane



United States Patent 3,525,603 METHOD OF INCREASING THE SUGAR CONTENT OFSUGAR CANE Philip C. Hamm, Glendale, Mo., assiguor to Monsanto Company,St. Louis, Mo., a corporation of Delaware No Drawing.Continuation-impart of application Ser. No. 582,223, Sept. 27, 1966.This application Oct. 21, 1968, Ser. No. 769,407

Int. Cl. A01n 9/14 US. Cl. 71-103 12 Claims ABSTRACT OF THE DISCLOSUREIncreasing the sugar content of sugar cane by contacting the sugar canewith substituted benzenesulfonyl ureas and its salts.

This application is a continuation-in-part of application Ser. No.582,223, filed Sept. 27, 1966, now abandoned.

In accordance with this invention, the sugar content of sugar cane isincreased by a method which comprises applying to maturing sugar caneone or more compounds selected from the group consisting of (I)Compounds having the formula wherein X is selected from the groupconsisting of chloro, bromo, iodo and fiuoro; Y is selected from thegroup consisting of alkyl, alkoxy, alkenyl and alkynyl each of which hasa maximum of 12 carbon atoms; Z is selected from the group consisting ofN0 NH NO, CN and i NHCR wherein R is selected from the group consistingof hydrogen and alkyl having a maximum of 12 carbon atoms; a is aninteger from 0 to 5, inclusive; b is an integer from 0 to 3, inclusive;c is an integer from 0 to 1, inclusive; M is a salt-formnig cationselected from the group consisting of alkali metals, alkaline earthmetals, ammonium and aliphatic-substituted ammoniums; and n is thevalence of M, said compound being applied in an amount sufiicient toincrease the sugar content of the sugar cane but in an amountinsufficient to exert a herbicidal action.

In the above formula Y can be alkyl such as methyl, ethyl, n-propyl,isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, amyl, hexyl,heptyl, octyl, nonyl, decyl, dodecyl and the various homologues andisomers of alkyl having not more tan 12 carbon atoms, alkenyl such asvinyl allyl, n-butenyl-l, n-butenyl-2, n-pentenyl-Z, nhexenyl-Z,2,3-dimethylbutenyl-2, n-heptenyl, n-decenyl, n-dodecenyl and thevarious homologues and isomers of alkenyl having not more than 12 carbonatoms, alkynyl such as ethynyl, propargyl, 3-hexynyl and the varioushomologues and isomers of alkynyl having not more than 12 carbon atoms,and alkoxy such as methoxy, ethoxy, butoxy, hexoxy, heptoxy and thevarious homologues and isomers of alkoxy having not more than 12 carbonatoms. R as alkyl can be any of the alkyl listed above for Y.

The aliphatic-substituted ammonium salts are those prepared from lowmolecular aliphatic amines, i.e., having a molecular weight below about300, and more particularly the alkyl amines, alkylene amines and alkanolamines containing not more than 2 amine groups such as methylamine,ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine,sec-butylamine, namylamine, iso-amylamine, hexylamine, heptylamine,octylamine, nonylamine, decylamine, undecylamine, dodecylamine,tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine,heptadecylamine, octadecylamine, methylethylamine, methylisopropylamine,methylhexylamine, methylnonylamine, methylpentadecylamine,methyloctadecylamine, ethylbutylamine, ethylheptylamine,ethyloctylamine, hexylheptylamine, hexyloctylamine, dimethylamine,diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine,diisobutylamine, disec-butylamine, di-n-amylamine, diisoamylamine,dihexylamine, diheptylamine, dioctylamine, trimethylamine,triethylamine, tri-n-propylamine, triisopropylamine, tri-nbutylamine,triisobutylamine, tri-sec-butylamine, tri-namylamine, ethanolamine,n-propanolamine, isopropanolamine, diethanolamine,tri-N-ethylethanolamine, N-ethylpropanolamine, N-butylethanolamine,allylamine, nbutenyl-2-amine, n-pentenyl-Z-amine,2,3-dimethylbutenyl-Z-amine, dibutenyl-Z-amine, n-hexenyl-Z-amine, andpropylenediamine.

The preferred compounds are selected from the group consisting ofwherein X is selected from the group consisting of chloro, bromo, iodoand fluoro; a is an integer 0 to 2, inclusive; Y is selected from thegroup consisting of alkyl and alkoxy having a maximum of four carbonatoms; b is an integer 0 to l, inclusive; Z is selected from the groupconsisting of N0 NH and if NHCR wherein R is selected from the groupconsisting of hydrogen and alkyl having a maximum of 5 carbon atoms; 0is an integer O to 1, inclusive, M is selected from the group consistingof alkali metal, alkaline earth metal, ammonium and substituted ammoniumof the formula Hl 3R R R wherein R R and R are each independentlyselected from the group consisting of hydrogen, alkyl, alkenyl andhydroxyalkyl each having a maximum of 4 carbon atoms.

It is known that the anionic portion of the salts is a resonance hybridhaving the terminology of isourea and urea depending upon the chargelocation. For convenience the terminology of is-ourea" will be used inthis specification and appended claims to designate the salts of theresonance hybrid, and the term urea will be used to designate the freebase.

The ureas and isourea salts are applied to the maturing sugar cane priorto the time the sugar cane has reached maximum sugar content or thecomplete ripening thereof. The application of the ureas and isoureasalts to sugar cane is carried out at more than about one week prior 3to harvest but not more than about 4 months prior to harvest.Application not more than about 2 months prior to harvest isparticularly advantageous.

As mentioned hereinbefore, the ureas and isourea salts are applied in anamount suflicient to increase the sugar content of the sugar cane, butin an amount insufficient to exert a herbicidal action. Such amounts aredetermined by and dependent upon the particular urea or isourea saltselected, the method of application, the state and condition of growthof the sugar cane, and the climatic conditions. An increase in sugarcontent of sugar cane without herbicidal action is obtained in mostinstances by the application of the ureas or isourea salts in an amountfrom about 0.1 to about 10 pounds per acre. The preferred applicationrate is from about 3 pounds to about 7 pounds of isourea salt per acre.

The isourea salts useful in the methods of this invention and processesfor making them are well known in the art. They can be prepared byreacting an arylsulfonamide with a suitable cyanate. For example,potassium 1-(p-nitrobenzenesulfonyl) isourea can be prepared by heatingsubstantially equimolar amounts of p-nitrobenzenesulfamide and potassiumcyanate in the presence of an aqueous medium under reflux for about 8hours, cooling the reaction mixture and recovering the product byfiltration. More detailed procedures for the preparation of variousp-su'bstituted benzenesulfonylisourea salts are set forth in Martin etal. US. Pat. 2,411,661 (Nov. 26, 1946) and Haack US. Pat. 2,385,571(Sept. 25, 1945), and the disclosures thereof are incorporated herein byreference.

The following examples illustrate the invention. Parts and percent areby weight unless otherwise indicated.

EXAMPLE 1 Six month old sugar cane (Finder) plants grown undergreenhouse conditions at a temperature from about 70 F. to about 90 F.and 65% relative humidity are sprayed with acetone-water solutionscontaining a small amount of emulsifier and various amounts of calciuml-(p-nitrobenzenesulfonyl)isourea at a rate equivalent to about 70gallons of spray per acre. The sprays are applied at rates of one andten pounds of isourea salt per acre using Randomized Block with sixreplications of each application rate including control (no activeingredient). Harvesting is carried out three weeks after spraying andthe amount of sucrose is measured and recorded. Results and furtherdetails are given in Table I wherein results are expressed as a percentof the control.

TABLE I Total wt. of sucrose Application rate, lb./ acre: per stalkControl 100 EXAMPLE 2 TABLE II.PERCENT FRESH WEIGHT OF SUCROSE IN STALKSHarvest Application rate, lb./acre 4 weeks 8 weeks Control (0) 100 100.2 134 163 4 EXAMPLE 3 Repeating Example 1, usingp-aminobenzenesulfonylurea (A) or potassium 1-(pbromobenzenesulfonyl)-isourea (B) in place of the calcium derivative yielded the results, inpercent of the control, listed in Table III.

TABLE III Total Weight of Sucrose Per Stalk Application rate, lb./acre(A) Control (0) 100 l 117 109 121 104 128 103 calcium1-(p-chlorobenzenesulfonyl)isourea calcium 1- (p-methylbenzenesulfonyl)isourea sodium 1-(p-nitrobenzenesulfonyl) isourea sodium 1-(p-methoxybenzene sulfonyl)isourea magnesium1-(p-chlorobenzenesulfonyl)isourea magnesiumlp-butenyl-2-benzenesulfonyl isourea calcium1-(p-aminobenzenesulfonyl)isourea calcium1-(p-cyanobenzenesulfonyl)isourea sodium1-(p-chlorobenzenesulfonyl)isourea magnesium1-(3,4-dichlorobenzenesulfonyl) isourea potassium1-(p-nitrosobenzenesulfonyl)isourea sodium1-(pchlorobenzenesulfonyl)isourea calcium1-(3,4-dichlorobenzenesulfonyl)isourea calcium1-(p-acetylaminobenzenesulfonyl)isourea magnesium1-(p-nitrobenzenesulfonyl)isourea magnesium 1- 3,4,S-trichlorobenzenesulfonyl isourea barium1-(p-a-minobnezenesulfonyl)isourea magnesium1-(p-aminobenzenesulfonyl)isourea magnesium1-(3-aminobenzenesulfonyl)isourea ammonium1-(p-nitrobenzenesulfonyl)isourea ammoniuml-(2,4-dimethylbenzlenesulfonyl)isourea ethylamine salt ofp-nitrobenzenesulfonyl isourea diethylamine salt ofp-nitrobenzenesulfonyl isourea propylamine salt ofp-nitrobenzenesulfonyl isourea triethylamine salt ofp-nitrobenzenesulfonyl isourea N-methylethylamine salt ofp-nitrobenzenesulfonyl isourea ethanolamine salt ofp-nitrobenzenesulfonyl isourea diethanolamine salt ofp-nitrobenzenesulfonyl isourea ethanolamine salt ofp-aminobenzenesulfonyl isourea allylamine salt of p-nitrobenzenesulfonylisourea ethanolamine salt of p-acetylaminobenzenesulfonyl isoureadiethylamine salt of n-butylcarbonylaminobenzenesul fonyl isoureap-aminobenzenesulfonyl urea p-nitrobenzenesulfonyl ureap-chlorobenzenesulfonyl urea 3 ,4-dichlorobenzenesulfonyl ureap-nitrosobenzenesulfonyl urea p-acetylbenzenesulfonyl ureap-cyanobenzenesulfonyl urea 3,4,S-trichlorobenzenesulfonyl ureap-methylbenzenesulfonyl urea p-methoxybenzenesulfonyl urea2,4-dimethylbenzenesulfonyl urea p-n-buteny1-2-benzenesulfonyl urea Forthe sake of brevity, the term active ingredien is used hereinafter inthis specification to describe the ureas and isourea salts useful inaccordance with the methods of this invention.

In practicing the methods of this invention, the active ingredients canbe used alone or in combination with an adjuvant in liquid or solidform. The compositions are prepared by admixing the active ingredientwith an adjuvant including diluents, extenders, spreaders, adhesives,carriers and conditioning agents to provide compositions in the form offinely-divided particulate solids, solutions, dispersions or emulsions.Thus the active ingredient. can be used with an adjuvant such as afinelydivided particulate solid, at liquid of organic origin, water, a.wetting agent, dispersing agent, an emulsifying agent or any suitablecombination of these.

Typical finely-divided solid carriers and extenders which can be used inthe compositions of this invention include, for example, the tales,clays, pumice, silica, lime, calcium carbonate, diatomaceous earth,quartz, fullers earth, salt, sulfur, powdered cork, powdered wood,cotton seed hulls, wheat flour, soybean flour, walnut flour, chalk,tobacco dust, volcanic ash, charcoals and the like. Typical liquiddiluents include for example, water, kerosene, Stoddard solvent, hexane,benzene, toluene, acetone, ethylene dichloride, xylene, alcohols, dieseloil, glycols and the like.

The compositions useful in this invention, particularly liquids andwettable particles, usually contain as a conditioning agent one or moresurface-active agents in amounts sufficient to render a givencomposition readily dispersible in water or in oil. By the termsurface-active agenf it is understood that wetting-agents, dispersingagents, suspending agents and emulsifying agents are included therein.

Preferred compositions containing the active ingredients have beendeveloped so that the active ingredients can be used to the greatestadvantage to increase the sugar content of sugar cane. The preferredcompositions comprise certain wettable powders, aqueous suspensions,dust formulations, emulsi'fiable oils and solutions in solvents. Ingeneral these preferred compositions all contain one or moresurface-active agents.

Surface-active agents which can be used in the compositions useful inthis invention are set out, for example, in Searle US. Pat. 2,426,417,Todd US. Pat. 2,655,447, Jones US. Pat 2,412,510 and Lenher US. Pat.2,139,276. A detailed list of such agents is also set forth by J. W.McCutcheon in Soap and Chemical Specialties, November 1947, page 8011 etseq., entitled Synthetic Detergents; Detergents and Emulsifiers-Up toDate (1960), by J. W. McCutcheon, Inc., and Bulletin E-607' of theBureau of Entomology and Plant Quarantine of the U.S.D.A. In general,less than 50 parts by weight of the surface-active agents is present per100 parts by weight of the composition.

Wettable powders are water-dispersible compositions containing one ormore active ingredients, an inert solid extender and one or more wettingand dispersing agents, The inert solid extenders are usually of mineralorigin such as the natural clays, diatomaceous earth and syntheticminerals derived from silica and the like. Examples of such extendersinclude kaolinites, attapulgite clay and synthetic magnesium silicate.

Preferred wetting agents are alkali metal alkylaryl sulfonates, sulfatedfatty alcohols, amines or acid amides, long chain acid esters of sodiumisethionate, esters of sodium sulfosuccinate, sulfated or sulfonatedfatty acid esters, petroleum snlfonates, sulfonated vegetable oils,ditertiary acetylinic glycols, polyoxyethylene derivatives ofalkylphenols (particularly isooctylphenol and nonylphenol) andpolyoxyethylene derivatives of mono-higher fatty acid esters of hexitolanhydrides (e.g. sorbitan). Preferred dispersants are methyl cellulose,polyvinyl alcohol, sodium lignin sulfonates, polymeric alkyl naphthalenesulfonates, sodium naphthalene sulfonate, polymethylenebisnaphthalenesulfonate and sodium N-methyl- N-(long chain acid)taurates.

The wettable powder compositions usually contain from about to about 95parts of active ingredient, from about 0.25 part to about 25.0 parts ofwetting agent, from about 0.25 part to about 7 parts of dispersant andfrom about 4.5 to about 94.5 parts of inert solid extender, all partsbeing by weight of the total composition. Where required from about "0.1to 2.0 parts by weight of the solid inert extender can be replaced by acorrosion inhibitor or antifoaming agent or both. If the particularactive ingredient selected is water-soluble, the solution formed byadmixture with water or other aqueous media can be employed in themethods of this invention without further formulation.

Emulsifiable oils are usually solutions of active ingredient inWater-immiscible solvents together with a surfactant. Suitablesurfactants are anionic, cationic and nonionic such as alkylarylpolyethoxy alcohols, polyethylene sorbital or sorbitan fatty acidesters, polyethylene glycol fatty esters, fatty alkylol amidecondensates, amine salts of fatty alcohol sulfates together with longchain alcohols and oil soluble petroleum sulfonates or mixtures thereof.The emulsifiable oil compositions generally contain from about 5 toparts active ingredient, about 1 to 50 parts surfactant and about 4 to94 parts solvent, all parts being by weight based on the total weight ofemulsifiable oil.

When operating in accordance with the present invention, effectiveamounts of the active ingredients are applied to sugar cane plants inany convenient fashion. The application of the compositions to the sugarcane can be carried out by conventional methods, e.g., power dusters,boom and hand sprayers and spray dusters. The compositions can also beapplied from airplanes as a dust or a spray because of theireffectiveness at low dosages.

Herbicidal compositions containing as an active ingredient therein manyof the above ureas and isourea salts are disclosed and claimed incopending application Ser. Nos. 210,220 and 210,242, both filed July 16,1962, and copending application Ser. No. 406,884, filed Oct. 25, 1964,which in turn is a division of application Ser. No. 210,217, filed July16, 1962, and now abandoned.

The terms amine and aliphatic substituted ammonium as used herein meanonly those ammonium and amine compounds wherein each valence of thenitrogen atom is attached to a different hydrogen or carbon atom.

Although the invention is described with respect to speci'ficmodifications, the details thereof are not to be construed aslimitations except to the extent indicated in the following claims.

While the illustrative embodiments of the invention have been describedhereinbefore with particularity, it will be understood that variousother modifications will be apparent to and can readily be made by thoseskilled in the art without departing from the scope and spirit of theinvention.

What is claimed is:

1. Method of increasing the sugar content of sugar cane which comprisesapplying to sugar cane a compound selected from the group consisting ofcompounds having the formula (a) o o W LNHtN...

and

wherein R is selected from the group consisting of chloro, bromo,fluoro, iodo, nitro and NH M is a salt-forming cation selected from thegroup consisting of alkali metals, alkaline earth metals, ammonium andsubstituted ammonium of the formula wherein R R and R are eachindependently selected from the group consisting of hydrogen, alkyl,alkenyl and hydroxyalkyl each having a maximum of 4 carbon atoms; and nis the valence of M, said compound being wherein R is selected from thegroup consisting of chloro, bromo, fiuoro, iodo, nitro and NH 6. Methodof claim 5 wherein the compound is paminobenzenesulfonyl urea.

7. Method in accordance with claim 1, in which the compounds have theformula ll 0 D wherein R is selected from the group consisting ofchloro, bromo, fluoro, iodo, nitro and NH M is a salt-forming cationselected from the group consisting of alkali metals, alkaline earthmetals, ammonium and substituted ammonium of the formula wherein R R andR are each independently selected from the group consisting of hydrogen,alkyl, alkenyl and hydroxyalkyl each having a maximum of 4 carbon atoms;and n is the valence of M.

8. Method of claim 7 wherein the compound is calcium1-(p-nitrobenzenesulfonyl)isourea.

9. Method of claim 7 wherein the compound is calcium 1-(p-aminobenzenesulfonyl isourea.

10. Method of claim 7 wherein the compound is calcium1-(p-chlorobenzenes'ulfonyl)isourea.

11. Method of claim 7 wherein the compound is the ethanolamine salt ofp-nitrobenzenesulfonyl isourea.

12. Method of claim 7 wherein the compound is potassium1-(p-bromobenzenesulfonyl)isourea.

References Cited UNITED STATES PATENTS 3,307,932 3/1967 Guyot 7185FOREIGN PATENTS 634,962 l/1963 Belgium.

JAMES O. THOMAS, 111., Primary Examiner

